How Solvation Energetics Dampen the Hydrogen Evolution Reaction to Maximize Zinc Anode Stability
How Solvation Energetics Dampen the Hydrogen Evolution Reaction to Maximize Zinc Anode Stability
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DOI：
10.1002/aenm.202303998
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发表时间：
2024-02
影响因子：
27.8
通讯作者：
Kingshuk Roy;Ashutosh Rana;Tushar K. Ghosh;Joseph N Heil;Sayan Roy;Kathryn J. Vannoy;Brian M. Tackett;Ming Chen;J. Dick
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文献类型：
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作者：
Kingshuk Roy;Ashutosh Rana;Tushar K. Ghosh;Joseph N Heil;Sayan Roy;Kathryn J. Vannoy;Brian M. Tackett;Ming Chen;J. Dick
水性锌金属电池（AZMB）正在成为目前流行的锂离子电池技术的一种有前途的替代品。然而，由于枝晶形成、析氢反应（HER）和阳极氧化锌钝化等挑战，AZMBs的发展受到阻碍。在此，合理设计了用于抑制HER、枝晶形成并增强循环性能的四烷基磺酰胺（TAS）添加剂。通过 67 Zn 和 1H 核磁共振波谱、高分辨率质谱 (HRMS) 和密度泛函理论 (DFT) 研究证明，只有 1 mm TAS 可以有效地从 Zn2+ 溶剂化壳中置换水分子，从而改变 Zn2+ 溶剂化基质并破坏自由水的氢键网络。伏安法与电极表面的原位监测同步显示，在 TAS 存在的情况下，枝晶生长和 HER 受到抑制。电化学质谱 (ECMS) 捕获锌电沉积过程中的实时 HER 抑制，揭示了 TAS 将 HER 抑制一个数量级的能力。在 TAS 存在下循环的纽扣电池中，循环寿命提高了约 25 倍，从约 100 小时延长至超过 2500 小时。此外，通过抑制钝化产物的形成，证明该策略可以最大限度地提高锌金属阳极的稳定性。
Aqueous zinc metal batteries (AZMB) are emerging as a promising alternative to the prevailing existing Lithium‐ion battery technology. However, the development of AZMBs is hindered due to challenges including dendrite formation, hydrogen evolution reaction (HER), and ZnO passivation on the anode. Here, a tetraalkylsulfonamide (TAS) additive for suppressing HER, dendrite formation, and enhancing cyclability is rationally designed. Only 1 mm TAS is found that can effectively displace water molecules from the Zn2+ solvation shell, thereby altering the solvation matrix of Zn2+ and disrupting the hydrogen bond network of free water, as demonstrated through 67 Zn and 1H nuclear magnetic resonance spectroscopy, high‐resolution mass spectrometry (HRMS), and density functional theory (DFT) studies. Voltammetry synchronized with in situ monitoring of the electrode surface reveals suppressed dendritic growth and HER in the presence of TAS. Electrochemical mass spectrometry (ECMS) captures real‐time HER suppression during Zn electrodeposition, revealing the ability of TAS to suppress the HER by an order of magnitude. A ≈25‐fold cycle life improvement from ≈100 h to over 2500 h in coin cells cycled in the presence of TAS. Furthermore, by suppressing passivation product formation, it is demonstrated that strategy robustly maximizes the stability of Zn metal anodes.